Method for recovering and/or recycling material

ABSTRACT

A method for recovering and/or recycling starting silicon material by crushing the starting material. The recovered or recycled material is melted, and crystals, e.g. as a silicon block, tube, or strip, are grown from the obtained melt. To use starting materials that have a high aspect ratio to be able to convey the same without any problem, broken polycrystalline needle-shaped Si material (material I) containing particles having an aspect ratio A I , 5&lt;A I ≦30, is used as a starting material. Material I is crushed so that the crushed particles (material II) have an aspect ratio A II &lt;3. Alternatively, a broken Si wafer is used that is composed of laminar particles which are crushed so that the crushed particles (material III) have an aspect ratio A III &lt;3.

The invention relates to a method for recovering and/or recycling lumpy silicon starting material by crushing the starting material, whereby the recovered or recycled material is melted, and from this melt, crystals are grown as silicon block, tube, or strip, for example.

To produce silicon crystals, large waste pieces are normally used, such as fragments or chunks left over from poly-Si production, sawed-off end pieces of Czochralski or float-zone crystals, edge pieces from discarded blocks, and spherical or splinter-shaped broken material.

With Si-block casting technique, fine Si-granulate is required in order to fill gaps and hollow spaces during the filling of crucibles, in order to achieve high filling rates.

With the Czochralski (CZ) production technique, Si-chunks (large pieces with a diameter of several centimeters) are used for charging. For post-charging, some spherical material with a particle size of 0.2-5 mm is also used. Such particles are normally produced using a fluidized bed separation method. With this material, which is approximately one millimeter in size, considerably finer gradation is achieved in charging.

Also with the edge-defined film-fed growth (EFG) method, in which Si-wafers in the form of polygonal tubes are drawn directly out of the melt, a granulate with a particle-size in the millimeter range is used, because due to the crucible volume, finer charging is required. In the state of the art, spherical material is currently used exclusively.

In addition to this spherical material, there are also irregularly shaped particles of the corresponding size that can be produced by breaking them off solid polycrystalline silicon. This material shows a percentage of approximately 0.1% to 10% (mean value 1%) due to the production method (pyrolytic growth from the gas phase on a rod), a distinctly elongate structure with a high aspect ratio (length to smallest upward measurement; hereinafter the simplified ratio of length to width will be used). This substance is recognizable from the material containing needles with an aspect ratio (length:width) that is much higher than 1, as well as particles with an aspect ratio of 10-30. These can only be filtered out only with difficulty. But the elongate structure is disadvantageous when conveying through pipes with a small diameter or those that have curves and corners.

From WO-A-2005/088680, a method is known for conveying solids particles of irregular geometry that have a large aspect ratio and can be conveyed through pipes by first adding solid particles with a regular geometrical form. In order to ensure unobstructed conveyance, the solids particles with an irregular geometrical form should have a aspect ratio of ≦3.

Recycled Si-block remainders, chunks, and sections of Cz crystals, due to their size, create hollow spaces in the bulk material, so that the bulk density is relatively low. These hollow spaces are therefore filled with finer, and as stated above, often spherical material.

U.S. Pat. No. 4,084,024 describes a method of producing high purity silicon. The silicon material produced displays a uniform geometry. In order to produce single crystal silicon blocks with the required doping, according to WO-A-86/06764, mixtures of different silicon starting materials are used.

According to U.S. Pat. No. 5,304,241, a powder mixture consisting of silicon dioxide is used as a filler for a sealing agent for electronic components. In order to obtain the pulverized material, silicon dioxide particles are crushed using a pulverizer, which is lined with a ceramic layer in order to avoid contamination. The aspect ratio of the pulverized particles ranges from 1.2 to 1.4.

The object of the present invention is to develop a method of the initially cited type, so that starting materials that contain needles with a high aspect ratio will be suitable, on the one hand, for conveyance without causing problems, particularly through pipes with a small diameter or pipes with angles, and on the other hand, will be suitable for use in post-charging in melts to the required extent because of their bulk density.

In order to achieve this object, the invention essentially provides that as starting material, either crushed polycrystalline silicon material that has at least some percentage of needle-shaped particles (material I) that have an aspect ratio of A_(I) with 5<A_(I)≦30, is used, whereby the material I is crushed in such a way that the crushed particles (material II) essentially have an aspect ratio A_(II)<3, or a broken Si-wafer is used which consists of laminar particles that are crushed in such a way that the crushed particles (material III) essentially have an aspect ratio of A_(III) with A_(III)<3. Material I can be a silicon extracted from the gas phase or a melt.

In accordance with the invention, a silicon material is crushed and broken in order to obtain a higher percentage of particles with a uniform aspect ratio of A_(II) with A_(II)<3. This is done through targeted crushing, particularly in a cutting mill. Through the processing of the material I, and the smaller and more uniform aspect ratio of the material II that is achieved, there is the advantage that transport through curves and around corners or through a pipe of a smaller diameter is possible without the necessity of adding particles with regular external geometry. In addition, compared with the material I, there is a 10% to 20% higher layer density, which enables more compact filling of crucibles and ingot molds.

Alternatively, there is the possibility of using broken Si-wafer as the starting material for recycling, using a conveyable Si-granulate of doped and/or non-doped laminar silicon material, such as broken, rejected silicon wafer from sawn Czochralski wafers or multi-crystalline block casting methods, as well as wafers cultured according to the EFG method, or corner and edge waste from a polygon resulting from an EFG process or another strip-drawing process, for example ESB or the RSG method (ribbon growth substrate), or from crystalline wafer generally. The milled broken Si-wafer, whose particles essentially have an aspect ratio of A_(III) with A_(III)<3, preferably A_(III)≈1, can be returned to the wafer-producing loop, whereby recycling based on the inventive idea is high-purity recycling, as explained below.

In order to provide charging material with the required doping, the mixing of recycled starting material with known doping in the required scope is provided. For producing material III in particular, it is provided that broken wafer is presorted and collected separately, for example in barrels, whereby presorting is done according to the characteristics of the starting material.

This is followed by an appropriate classification of the starting materials, whereby for example, broken wafer is collected and stored separately according to resistance group and/or degree of purity. In a further development of the invention, there is the possibility of collecting material based on doping or origin or the original production method, so that the materials whose doping is uniform within a desired range, or whose origin or production method is the same, are assigned to one class. Aside from that, the allocation and class type are defined by the intended purpose.

In this way, a corresponding material class can be defined, even when the material contains macroscopically visible contaminants. Surplus silicon resulting from the cutting of an EFG octagon, for example, can sometimes contain elements that cannot be removed immediately, at the start of a process. However, these elements can be removed before further processing, so that the material is purified before the next process.

The systematic collection of starting material by classes can also be done after crushing, in order to subsequently be able to produce a charging material with the desired qualities through the mixing of materials from different classes.

It is provided in particular that the material III, which features an essentially polygonal laminar geometry, has a maximum length L of 0.1 mm≦L≦10 mm, preferably 0.5 mm≦L≦3 mm and/or a thickness D of 0.5 mm≦D≦3 mm, preferably 0.1 mm≦D≦0.6 mm.

As material III, a material should preferably be used that has a volume resistance R_(v) with 1 μΩcm≦R_(v)≦2000 Ωcm.

A further development of the invention provides for the crushing to be done by crushing machines that preferably operate with a rotating crushing tool. For flat material samples, such as broken wafer, a cutting mill is preferably used, regardless of the wafer size.

A cutting mill is also suitable for relatively flat and needle-shaped granulate with dimensions ranging from 1 cm to 3 cm, i.e. for material I, or material II. Large or voluminous, solid waste pieces will preferably be conveyed to jaw crushers, in order for them to crush the material to a size that is then suitable for a cutting mill.

Regardless of the means employed, crushing takes place to an extent that will allow subsequent reuse. The crushing process is carried out in such a way that the production of large amounts of silicon dust or an accumulation of silicon dust in the product is avoided. Such silicon dust would result particularly from grinding processes, so grinding and abrasion is avoided in the crushing process. In the case of chopping and crushing of materials, however, there is little dust accumulation.

Irrespective of the means used, the crushing machine should reduce the particle size of the starting material in such a way that the particle, in the direction of its longest extent, measures no more than 10 mm, and preferably 5 mm.

In order to ensure that there is no uncontrolled contamination of the recycled material during crushing—this can occur through erosion of the internal walls of the crushing tool or cutting mill—it is provided that at least the internal walls of the crushing device are lined with a silicon material or a mechanically stable and scratch-resistant ceramic compound, such as SiC, SiN, or WC (solid). Layers can also be applied by means of a thermic spray-coating process, plasma spraying, a vacuum process, etc. Preferably, however, these are solid walls with a thickness of between 0.5 mm and 50 mm, preferably between 5 mm and 10 mm, made of pure silicon or sintered or solid CVD-coated SiC or Si₃N₄. The linings can be applied to the internal walls with a suitable fixing material such as an adhesive, which ensures that if the linings wear off, only material from the wall lining will be mixed into the material to be crushed and recycled, and that there will be no metal contamination from the body of the crushing machine itself.

An alternative proposal provides for the wall to be lined with an abrasion-resistant synthetic material, such as Vulkollan®, Teflon®, Halar® and/or polyoximethylene.

In order to avoid contamination of the recycled material, it is further provided that the crushed starting material be discharged from the cutting mill without passing through a screen, such as a perforated metal plate, as is otherwise usual.

In that way, contamination is avoided which, in the state of the art, occurs because the size of the crushed material is determined by the apertures in a perforated metal plate or screen through which the material is discharged from a cutting mill. The corresponding plate or screen is subject to wear, because the crushed Si-particles constantly abrade material from the perforated metal plate or screen, and from the wear protection coating applied to it.

The percentage of particles of maximum extension (length in material II or a diagonal in material III) depends on the rotational speed of the cutting or rotor knife (FIG. 6). In order to achieve this, the corresponding crushing machines are operated at higher rotational speeds than those of normal operation, whereby preferred rotational speeds between 500 revolutions/min. and 4000 revolutions/min. are specified in the case of a cutting mill, and for producing material II, preferably 3000 to 3500 RPM, and for producing material III, preferably 2000 to 2500 RPM.

According to an additional proposal of the invention, it is provided that material is crushed by putting the starting material in a receptacle such as a drum made of a synthetic material, and the receptacle is then put in rotary motion. For this purpose, the receptacle, such as a barrel, can be placed on a roller block and then made to revolve about its axis using the roller block. Due to the revolving motion, the material in the receptacle will be put under constantly varying load and thus crushed. The crushing effect can be intensified by inserting a round Czochralski-drawn solid cylinder, for example, or an angularly-sawn solid body of silicon into the receptacle, whereby the solid cylinder, or the solid body, because of its weight and rolling motion, will put constant load on the starting material and crush it.

Owing to the use of synthetic material for the receptacle, the crushed material has a high degree of purity, because no metallic material enters it from the walls. The fine dust that results from grinding motions should be immediately removed from the interior of the receptacle during the crushing process. This can be done by covering one or more of the openings in the receptacle with a screening fabric for the largest allowable particle (for example, mesh widths of 1 to 3 mm). In that way, the fine particles fall through the mesh and out of the receptacle and cannot be crushed to an even smaller size. The production of fine dust is therefore prevented.

In addition, it is possible to continuously add material to the receptacle, so that continuous operation is possible. It is provided in particular that an automatic feeding device be used, with continuous feeding from the axis of symmetry of the revolving receptacle, whereby Si, for example, can be fed in the amount required by the specified rotational speed.

Immediately after crushing, the material is divided into suitable grain-size fractions by a sieving machine, for example 0≦KG 1 (under-dimensioned particles)≦0.3 mm/0.3 mm≦KG 2 (product fraction)≦3.0 mm/3.0 mm≦KG 3 (over-dimensioned particles).

Other details, advantages, and characteristics of the invention become evident not only from the claims and the characteristics derived from them, individually or in combination, but also from the explanations supplied with the drawings.

They show:

FIG. 1 Aspect ratio of material to be recycled, or recycled material,

FIG. 2 Photographs of grain shape and etching figure of a material to be recycled,

FIG. 3 Photographs of grain shape and etching figure of a recycled material,

FIG. 4 Photographs of grain shape and etching figure of an additional material,

FIG. 5 Photographs of grain shape and etching figure of an additional material,

FIG. 6 A schematic representation of grain-shape distribution depending on the rotational speed of a cutting tool, and

FIG. 7 a schematic diagram of a cutting mill.

The characteristics of the materials to be recycled, or the materials that have been recycled in accordance with the invention, said materials being intended for charging melts from which silicon crystals will be grown, will be explained with reference to figures or to the photographs and etching figures they contain. The crystals can be produced according to the Czochralski method or the EFG process, to name just a few production methods as examples.

According to the inventive teaching, irregularly shaped particles that can be produced by breaking them out of solid polycrystalline silicon, undergo further processing. Due to the production method (pyrolytic growth from the gas phase on a rod), the material has a distinctly elongate structure with a high aspect ratio (length to smallest measurement, hereinafter defined for the purpose of simplification as, length to width). The corresponding materials, which are produced from solid polycrystalline silicon, are characterized by the fact that the material contains needles that have an aspect ratio (length:width) of the needles that is much higher than 1, and that there are thus few particles with an aspect ratio of 10-30. These can only be screened out with difficulty, and this means that during the conveyance of the material that is called material I in this context, the corresponding particles have an obstructive effect, particularly when material is conveyed through pipes with a narrow diameter or through pipe bends and around corners.

In accordance with the invention, the material I is crushed and further processed in order to obtain a higher percentage of particles with a uniform aspect ratio A_(II)<3. This is done through targeted crushing with a cutting instrument such as a cutting mill.

In order to illustrate the differences in the aspect ratios of materials I and II, reference is made to FIG. 1. This shows the relative frequency of the particles according to aspect ratio. Verification itself is done using an optical particle-analysis device, even though the different geometric dimensions are already visible optically. One can see that the starting material composed of crushed polycrystalline silicon contains a not inconsiderable percentage of particles whose aspect ratio is higher than 10, lying particularly in the range of 10 to 30. If the material is crushed in the manner described below, the aspect ratio can be reduced, namely to the value A_(II)<10. This results in better conveyance characteristics for the material II compared with material I.

Crushing the material I also produces a higher bulk density for material II and thus the possibility of more compact filling of a crucible or ingot mold. An additional characteristic of the material II is seen in the etching figure of an abraded silicon sample. FIG. 2 shows an abraded and chemically etched Si-particle, which is characterized by finely branched grain boundaries in the material. The material I is obtained through gas phase precipitation, whereby the grain-boundary gaps are dependent on precipitation conditions. The material II, which is derived from material I by crushing material I, can be recognized by the typical microstructure, which is identical to that of material I, as can be seen from FIG. 3. As a result, the differences between material I and material II are not in the microstructure, but rather in grain shape alone, whereby the material II has the smaller aspect ratio.

The crushed particles of material II, which are made from material I, predominantly display a less needle-shaped form and a rounder appearance, as FIG. 3 illustrates.

In accordance with the invention, however, not only polycrystalline silicon produced through pyrolytic growth from the gas phase is used for addition to a melt, but also material produced from broken Si-wafer. This involves a non-conveyable Si-granulate made from doped and/or nondoped laminar silicon material, such as broken or unbroken discarded silicon wafer that measures, for example, 156 mm×156 mm, 125 mm×125 mm, or 100 mm×100 mm, or fragments of the same, produced from sawn Czochralski wafers, or multi-crystalline block-cast wafers, as well as from wafers grown using the EFG process, and from corner and edge cuttings from a polygon from the EFG process, from other strip-drawing processes (for example ESP) or the RGS (ribbon growth substrate) method, as well as generally from single and multi-crystal wafers. According to the teaching of the invention, this wafer waste can be effectively reintroduced into the production cycle.

The aspect ratio can be determined with an optical particle analysis device. This shows an even lower aspect ratio (length:width) compared with the material II, as seen in FIG. 1. Values for the aspect ratio A_(III) are normally A_(III)<3, which is only exceeded in rare cases.

The material III is also characterized by a virtually constant thickness of at least a large percentage of the particles. In addition, through mechanical polishing and chemical etching, a typical grain and defect structure can be seen in material III, which is very obviously different from those of materials I and II, as a comparison of FIGS. 2 and 3 with FIGS. 4 and 5 demonstrates.

FIG. 5, left, shows material III, which is produced from recycled EFG wafers, as an example of a material drawn from a melt for further processing. The material has a slice thickness ranging from about 50 μm to 450 μm, preferably 250 μm-350 μm. It breaks into rectangular parts and displays the twin-grain formation that is very typical of the EFG process in a large number of particles (FIG. 4, right).

FIG. 5 in the left image shows a material III for further processing, which is produced from multi-crystalline wafers and those produced, for example, according to the block-casting method. The material has a wafer thickness of between 50 μm and 450 μm, preferably 250 μm-350 μm. It breaks into polygonal rectangular and triangular pieces and displays the formation of grain boundaries that is typical for the ingot-casting method, as the etching figure on the left demonstrates. It should be noted in this context that this grain-boundary structure is less often detected in the material, as the size of the crushed particles is below the grain-size typical of the material, of about 1 cm to 2 cm. Because the material preferably breaks at the grain boundaries, the grain structure can consequently be determined in only a few pieces in areas with a very small structure in the millimeter range.

Due to the polygonal form of the particles of the material III, a high bulk density can be achieved, that is 15% to 20% above the value of material I.

The table below shows the bulk and tap density of the materials I, II, and II, which are to be understood purely as examples.

TABLE 1 Bulk density and tap density Compact density Loose bulk (bulk (tap density) Material Aspect ratio density) [g/cm³] [g/cm³] Material I, screened 0.94 +/− 1% 1.15 +/− 4% (0.5-2.0 mm mesh width) Material II, 1.15 +/− 1% 1.19 +/− 4% screened (0.5-2.00 mm mesh width) Material III, 1.15 +/− 1.5% 1.35 +/− 0.2% screened (0.5-2.00 mm mesh width)

From the table, it can be seen that the bulk and tap density of recycled silicon of the material III results in flat wafers with a comparable screen fraction and 15 to 20 percent higher density than material I.

The materials I and II, due to the production technique (high-purity gas phase precipitation), are usually nondoped, although precipitation of doped polycrystals is in principle possible in the state of the art.

If remelt material is used as the starting substance for material I, the doping must be considered and determined beforehand. In this case, the materials I and II can be p- or n-conducting, depending on the doping of the starting material.

The material III can contain nondoped or doped, p-conducting and/or n-conducting particles. If the type and degree of the doping concentration of the starting material is known, the desired doping concentration can be adjusted through suitable mixing of grains of different concentration. The doping concentration can be determined by means of automated test assemblies (such as 4-peak measurement, thermo power, microwave reflection, IR absorption), but also through chemical analysis such as mass spectroscopy, AAS (atom absorption spectroscopy), TXRF (total reflection x-ray fluorescence analysis).

The desired doping of a material is achieved by adding calculated amounts of differently doped or nondoped material. In this way, it is possible to make a raw material with a desired overall dopant concentration by mixing different components. In this way, remainders of highly doped wafers, for example n, p>5×10¹⁸ cm⁻³, can be used directly to dope nondoped melts.

In order to produce material III, broken wafer of every possible type is collected in drums. It has been shown to be advantageous if materials are collected with the desired characteristics in mind in the early stage of accumulation, because at that point, knowledge of material qualities is still present.

Accordingly, suitable classification of the material should be undertaken during collection, so that material can be collected in an orderly way, classified according to resistance groups for example, or according to doping percentage, or purity class. In that way, for example, materials can be collected by resistance groups, whereby resistance conforms within a factor of 2. The division into classes and class characteristics will be determined by the intended end use of the material.

Even when the material contains macroscopically identifiable impurities, a corresponding material class can be determined for it. For example, silicon left over from cutting EFG octagons sometimes contains components that cannot be immediately removed at the beginning of the process. However, these components can be removed before further processing, and thus the material can be purified before the process continues.

Through targeted collection of starting material according to classes with the same characteristics, material with the desired characteristics can be produced after crushing and mixing of this material.

Crushing takes place in a crushing machine, which preferably operates with a rotating crushing tool. In the case of flat material samples, such as broken wafer, a cutting mill will be used, irrespective of wafer size.

The cutting mill is suitable for use with relatively flat and needle-shaped granulate measuring up to 1-3 cm. For large or voluminous, solid waste pieces, jaw crushers, for example, are more suitable, by means of which the material can be crushed to a size that can be processed by the cutting mill. The object of this crushing process is to reduce the material only to the size at which it can subsequently be used. During the crushing process, the material is therefore reduced to dimensions ranging between a few millimeters and a few centimeters. The object of the crushing process is a grain size ranging from 0.1-20 mm, and preferably 0.3-3.0 mm

The production of silicon dust should be avoided as far as possible, or, action should be taken to counteract the accumulation of Si-dust in the product. Si-silicon dust is often produced by grinding processes, which is why abrasion and grinding should be avoided during the production process. On the other hand, chopping and breaking of materials is preferred, as there is then little dust production.

Because silicon, quartz glass, and ceramics are brittle and hard materials, there is a risk of contaminants entering through wear on the side walls of the crushing instrument, such as a cutting mill. As a standard measure, all wear-protection layers, for example tungsten carbide, are applied to the mill walls by means of thermal spraying methods or plasma spraying methods. However, these layers are worn off by hard materials like silicon during the crushing process, which leads to contamination concentrations of 1000 to 10,000 ppba of Fe, Ni, and WC, for example, depending on the structure of the wear-protection coating. The surface of the perforated screen that is normally mounted on the machine in order to screen out the crushed material is particularly subject to wear.

The solution to this problem is provided by coating the internal walls of the mill with a silicon material or a mechanically stable and scratch-resistant ceramic compound such as SiC, SiN, WC, or a hard metal (solid). Layers can naturally be applied using thermic spraying processes, plasma spraying in a vacuum, etc.

Better suited, however, are solid walls with a thickness of 0.5 to 50 mm, preferably 5-10 mm, made from pure silicon or sintered or solid CVD-precipitated SiC or Si₃N₄. When the material to be crushed consists of quartz glass, the wall lining consists of quartz plates. These wall linings are affixed to the wall with a strong adhesive and ensure that when there is abrasion of the wall, only the material making up the wall lining, but no metal contaminants, is introduced into the crushed material.

However, there is also the possibility of coating the wall with an abrasion-resistant synthetic material, such as Vulkollan®, Teflon®, Halar® and/or polyoximethylene.

Normally, in the case of a cutting mill, the size of the material to be cut is determined by the apertures in a perforated plate. However, such a plate is subject to wear, as the Si-particles are scraped across it, resulting in continual abrasion of the material making up the perforated plate and the wear-resistant coating applied to it. It is a feature of the invention that operation without the perforated plate, as it is subject to particularly heavy abrasion and can only be provided with a hard-material coating, not with a solid wall lining.

In one embodiment of the invention, therefore, the perforated plate is dispensed with. The size of the particles in the material that is cut is controlled instead by the rotational speed of the rotor knife. This results in a cutting method of higher than normal rotational speed. The dependence of the product of the high-speed rotational cutting mill is however strongly influenced by the shape of the grains put into it, particularly the grain thickness, but also the length of the grain.

The relatively large and thin charging material, broken wafer, which is used for producing material III, achieves higher yields even at lower rotational speeds than the smaller and thicker granulate (material I), from which material of the type II is produced (FIG. 6). The yield is adjusted primarily by means of the cutting-knife interval.

In general, the product-fraction yield increases with rotational speed, and the percentage of over-dimensioned particles decreases. The exact dependence for different materials must be determined for individual cases respectively.

Nevertheless, FIG. 6 basically reflects the conditions that apply to the change in product fraction and over-dimensioned particles of individual materials, which are dependent on the rotational speed of the cutting tool. The curves 1 and 2 apply to material III. The rising curve 1 shows the change relative to the product fraction, which increases as the rotational speed of the cutting tool increases. Accordingly, the curve marked 2 is characteristic of the undesirable over-dimensioned particle, i.e. the percentage of over-dimensioned particles decreases with an increase in the rotational speed.

Regarding the materials I/II, the curves 3 and 4 illustrate that the product fraction also increases with a higher rotational speed (curve 3), whereas the percentage of over-dimensioned particles (curve 4) decreases.

The more easily the material cleaves, the lower the rotational speeds that are necessary in order to obtain a high percentage of the desired particle size. The smaller the material that is introduced, in terms of maximum length, the higher the rotational speed must be in order to achieve the desired product fraction, and in that way minimize over-dimensioned particles.

The geometry of the material also determines the particle-size distribution achieved through the crushing process. Materials with a high aspect ratio require higher rotational speeds. Likewise, smaller, less easily cleavable particles require higher rotational speeds.

With an operating method that does not involve a perforated screen, the fine-particle fraction (under-dimensioned particles) can be drastically reduced to values under 1%. This is highly advantageous, because the finely crushed material, with grain sizes under 0.5 mm, due to its large surface area, absorbs more contaminant particles that adhere to the surface. With increasing rotational speed, and without a perforated plate, it was possible to increase the product-fraction yield to approximately 80%.

The purity of the product is significantly better without a perforated plate. Finally, less contaminating material is introduced into the wafer for two reasons:

-   -   1. Abrasion due to the perforated plate disappears entirely, so         that a large portion of the contaminants are not introduced.     -   2. Due to the smaller percentage of under-dimensioned particles,         there is less surface area.

Table 2 shows the improvement effect achieved by making certain changes. Lining the walls with silicon produces a significant reduction in the contamination concentrations of Fe and Ni, i.e. the materials that make up the cross beaters of the cutting mills. WC is also embedded in Fe and Ni. Dispensing with the perforated plate coated with WC results in a reduction in the tungsten-carbide concentration that is under the limit of detection. The WC is thereby embedded in a Fe, Ni-layer.

TABLE 2 Purity of products With wear- With protection (flame- Si-lining on With Si-lining and sprayed tungsten the walls and without perforated Contamination carbine coating) perforated plate plate Fe [ppba] 1000 200 <30 Ni [ppba] 200 50 <10 W [ppba] >1000 1000 <5

The material purity achieved in this way is high enough to produce solar-cell efficiency of more than 14% to 15%.

Another way to crush material is to put the silicon into a plastic drum on a roller block, the drum then revolving slowly due to the action of the roller block. Because the drum revolves, the material is subjected to constantly changing load, which breaks it up. The breaking effect can be markedly intensified by inserting a round, CZ-drawn, solid cylinder into the drum, or a jaggedly sawn, solid silicon body, because the crystal is constantly subjected to loads and breaks due to its weight and the rolling movements of the Si-material.

This material also has a high degree of purity, because no metallic material from the walls enters it. During the crushing process, fine dust resulting from grinding movements is removed as quickly as possible from the interior of the drum.

This is achieved by openings in the body of the drum that are covered by screening fabric with the mesh width of the largest allowable grain (for example, a mesh width of 1 mm-2 mm, preferably 3 mm). The fine grains fall through the mesh and out of the drum and cannot be ground any finer, and are available for the rest of the process. An automatic feeding device can be used, feeding from the axis of symmetry of the revolving receptacle. In this case, as much Si is added to the drum as needed in order to maintain continuous operation at a specified speed.

Immediately after crushing, the material is divided into suitable grain-size fractions by a screening machine, for example 0≦KG 1 (under-dimensioned particles)≦0.3 mm/0.3 mm≦KG 2 (product fraction)≦3.0 mm/3.0 mm≦KG 3 (over-dimensioned particles).

The concepts of material recycling, or recycled material, mentioned above also include the recovery of materials that are melted in order to grow crystals. In other words, the starting material does not necessarily have to be previously used silicon material.

In addition, the invention is not restricted to the material that is crushed into materials II and III being added to a melt, even though that is preferably the case. Rather, the invention also applies to materials II and III, which are put into a crucible, without a melt already being in it.

FIG. 7 is a schematic diagram of a cutting mill 10, by means of which the materials I and III are crushed to an extent such that the desired aspect ratio of less than 3 is achieved, whereby the production of dust that causes contamination is minimized. At the same time, there is the possibility of any dust produced being vacuumed up into explosion-proof suction devices, for example.

The cutting mill 10, which in the schematic depiction is shown with a cuboid interior space 11 that merges into a funnel 13, features a housing 12 that consists of metal, preferably aluminum. An interior space 11 with a cuboid geometrical shape is formed by four approximately 2 cm thick wall plates 14, 16, which are screwed to the housing 12. The internal walls of the housing 12, i.e. the plates 14 and 16, are lined with about 5 to 10 mm thick silicon plates 18, 20, 22, 24. This can be done by gluing the silicon plates 18, 20, 22, 24 onto the aluminum plates 14, 16. This requires that the interior surfaces of the walls 14, 16 are even.

In the interior space 11 that is surrounded by the plates 14, 16, a cutting tool 28 is rotatably arranged. The cutting tool 28 is a rotational body 30 that takes the form of a multi-sided column that preferably has a triangular, quadrangular, or hexangular base area. The longitudinal surfaces of the rotational body 30 are clad with 5 mm to 100 mm thick silicon plates 32, 34, 36. In the embodiment shown, the rotational body takes the geometrical form of a triangular column.

Cutter bars 38, 40, 42 are affixed to the silicon plates 32, 34, 36, said cutter bars preferably consisting of solid tungsten carbide or silicon-infiltrated hard material. The cutter bars 38, 40, 42, are preferably screwed to the rotational body 30 by means of screws. The silicon plates 32, 34, 36 contain the corresponding boreholes. The screw heads are countersunk into the blades 38, 40, 42, and the exposed surfaces are covered with Teflon tape.

Further, the blades 44 and 46 extend from the lateral walls, which run parallel to the longitudinal edges of the rotational body 30 and are marked with the reference numerals 14 and 16, or from their liners 18, 20, 22, 24. The blades likewise consist of solid tungsten carbide and are directly secured to the lateral walls 16 and 18.

The gap between the blades 44, 46 and the longitudinal edges of the rotational body 30 that moves past them, or the cutter bars 38, 40, 42 that emerge from said edges, can be adjusted. For this purpose, the blades 44, 46, which feature a cuboid geometrical form, are welded to steel parts 50, 52, which are affixed by means of screws that pass from the outside through the housing walls 14, 16. The gap can then be adjusted by means of spacers that are not further described.

The blades 44, 46 are positioned or countersunk between the linings 18, 20, 22, 24, so that the material that is to be crushed or broken, comes into contact only with silicon and tungsten carbide.

In addition, the cutter bars 38, 40, 42 and/or the blades 44, 46 that emerge from the rotational body 30 should be beveled to about 400 μm, in order to avoid nicking.

In contrast to conventional cutting mills, at the outlet of the funnel 13 there is no perforated plate, which could otherwise be a source of contamination.

The rotational body 30 itself rotates at high speeds ranging between 500 rpm to 4000 rpm, in order to achieve the desired breaking or crushing of the materials that are to be added.

The advantage of the inventive arrangement is an obviously smaller portion of under-dimensioned particles (smaller than 0.3 to 0.5 mm), which are usually highly contaminated, and must be discarded. Without a perforated plate, the percentage is between 1% and 10%, whereas when the usual perforated plate used, the portion of under-dimensioned particles would lie between 10% and 20%, as measurements have shown.

In order to crush the materials I to III, they are added via a headside funnel 54. In the area of the funnel 54, the walls are also lined with silicon plates that are between 5 mm and 10 mm thick.

While the housing 12 is preferably completely lined with silicon material, it is also possible that less-stressed surfaces can have plastic plates. The corresponding plastic plates are also glued or screwed into place.

The material that falls through the cutting mill 10 is chopped between the blades 38, 40, 42, and 46, 48, which are composed of tungsten carbide, and then falls into the lower funnel 13, which is also lined with silicon, silicon carbide, or with silicon-infiltrated hard-material, or with plastic plates.

From there, the material can be conveyed to a screening machine, which screens out the fractions (for example, under-dimensioned particles <0.3 mm; product fraction 05 mm to 3.0 mm; over-dimensioned particles >3 mm) that are required for the subsequent processes. The corresponding values are just examples and can vary depending on the case of use. The dust that collects is suctioned away.

Depending on the dimensions of the cutting mill 10, throughputs of 30 kg/h, 100 kg/h or more are possible. 

1. A method for recovering and/or recycling silicon starting material by crushing the starting material, whereby the recovered or recycled material is melted, and from the melt produced in this way, crystals are grown, for example as silicon block, tube, or strip, characterized in that as starting material, either broken polycrystalline, at least partially needle-shaped Si-material (material I) is used, which contains particles that have an aspect ratio A_(I) with 5<A_(I)≦30, whereby the material I is crushed in such a way that the crushed particles (material II) essentially have an aspect ratio of A_(II)<3; or a broken Si wafer consisting of laminar particles is used, which is crushed in such a way that the crushed particles (material III) essentially have an aspect ratio of A_(III) with A_(III)<3.
 2. A method according to claim 1, characterized in that the material I is crushed is such a way that the material II has a bulk density that is 10% to 20% higher than that of material I.
 3. A method according to claim 1 or 2, characterized in that the material I is crushed in a cutting mill.
 4. A method according to at least one of the previous claims, characterized in that the material to be fed into the melt has a desired doping as a result of mixing specified amounts of recycled starting materials with known doping.
 5. A method according to at least one of the previous claims, characterized in that the starting material used to produce the material III is collected separately according to material characteristics, such as volume resistance or doping.
 6. A method according to at least one of the previous claims, characterized in that the crushing of the starting materials is done through the use of a rotating crushing tool that that breaks up, chops, or cracks the starting material.
 7. A method according to at least one of the previous claims, characterized in that a cutting mill is used as the crushing tool.
 8. A method according to at least one of the previous claims, characterized in that the crushing tool, at least as regards the walls of this device that come into contact with the starting material, is configured in such a way that a lining or coating is provided that prevents or essentially prevents contamination of the material to be crushed.
 9. A method according to at least one of the previous claims, characterized in that at least the interior walls of the crushing tool have a layer made of Si, SiC, SiN and/or solid WC.
 10. A method according to at least one of the previous claims, characterized in that, as a coating, solid walls are used with a thickness of 0.5 mm to 50 mm, preferably 5 mm to 10 mm that are made of pure silicon or sintered or solid CVD-precipitated SiC or Si₃N₄, or WC.
 11. A method according to at least one of the previous claims, characterized in that the crushed starting material is removed from the cutting tool without the use of a screen, such as a perforated plate.
 12. A method according to at least one of the previous claims, characterized in that the percentage of useable material II or useable material III is determined by the rotational speed of the rotating cutting tool.
 13. A method according to at least one of the previous claims, characterized in that in order to increase the percentage of useable material II or material III, the rotational speed RPM of the cutting tool, such as a cutting blade, is set at 500 RPM to 4000 RPM, preferably 3000 RPM to 3500 RPM for extracting the material II, and at 2000 RPM to 2500 RPM for extracting the material III.
 14. A method according to at least one of the previous claims, characterized in that the material III, which essentially features a polygonal, laminar geometry, has a maximum length L of 0.1 mm≦L≦10 mm, preferably 0.5 mm≦L≦3 and/or a thickness D of 0.05 mm≦D≦3 mm, preferably 0.1 mm≦0.6 mm.
 15. A method according to at least one of the previous claims, characterized in that as material III, a material is used that has a volume resistance R_(v) with 1 Ωcm≦R_(v)≦2000 Ωcm.
 16. A method according to at least one of the previous claims, characterized in that the walls of the crushing tool are lined with an abrasion-resistant plastic such as Vulkollan®, Teflon®, Halar® and/or polyoximethylene.
 17. A method according to at least one of the previous claims, characterized in that the starting material is placed in a preferably cylindrical receptacle, such as a drum, which is revolved in order to place alternating stress on the starting material.
 18. A method according to at least one of the previous claims, characterized in that in addition to the starting material, a solid body made of Si that acts on the starting material is put into the receptacle in addition to the starting material.
 19. A method according to at least one of the previous claims, characterized in that a solid cylinder or a four-cornered column is used as the solid body.
 20. A method according to at least one of the previous claims, characterized in that a receptacle with an opening covered by a screening fabric is used, through which opening the crushed starting material is removed.
 21. A cutting mill for crushing broken polycrystalline needle-shaped silicon material, which contains particles that have an aspect ratio of A_(I) with 5<A_(I)≦30, and/or broken Si wafer consisting of laminar particles, characterized in that the cutting mill (10) has an interior space (11) that is lined with silicon and/or plastic, that the cutting mill has rotational body (30) configured as a multi-sided column, that the interior space of the cutting mill is lined with silicon or features silicon, and that blades (46, 48) which run parallel with the longitudinal edges of the rotational body and are disposed in the rotational area of the rotational body, are arranged in the interior space of the cutting mill, and are adjustable with respect to the rotational body.
 22. A cutting mill according to claim 21, characterized in that the blades (46, 48) are composed of or contain tungsten carbide, silicon carbide or silicon-infiltrated hard material.
 23. A cutting mill according to claim 21 or 22, characterized in that cutter bars (38, 40, 42) made of solid tungsten carbide are arranged on the outer surfaces of the rotational body (30).
 24. A cutting mill according to at least one of the claims 21 to 23, characterized in that the cutting bars (38, 40, 42) extend from the longitudinal edges of the rotational body (30).
 25. A cutting mill according to at least one of the claims 21 to 24, characterized in that the cutting mill (10) has a free material outlet without a screen. 